Preparation of porous ZrO<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> macrobeads from ion-exchange resin templates

In this work, we will report a method to prepare porous ZrO₂ and ZrO₂/Al₂O₃ macrobeads using cation-exchange resins with sulfonate groups as templates. The preparation process involves metal ion-loading, ammonia-precipitation, and calcination at an appropriate temperature. Several characterization methods, such as TGA, XRD, SEM with EDX, TEM and N₂ adsorption and desorption, were used to characterize the ZrO₂ and ZrO₂/Al₂O₃ macrobeads. The results showed that the porous structures of the resin templates were negatively duplicated in the two kinds of macrobeads. We found the following interesting results: (1) The ZrO₂/Al₂O₃ macrobeads are composed of tetragonal zirconia nanocrystals that are more technologically important, while the pure ZrO₂ macrobeads consist of a mixture of tetragonal and monoclinic zirconia. (2) In the ZrO₂/Al₂O₃ macrobeads, the size of ZrO₂ nanocrystals is about 5 nm smaller than that (about 19 nm) found in the pure ZrO₂ macrobeads. (3) The ZrO₂/Al₂O₃ macrobeads have more mesopores and, therefore, have a larger surface area than the pure ZrO₂ macrobeads. These oxide macrobeads will have potential applications in catalysis by taking advantage of their macrobeads shape and pores structure.     

Ionic conductivity in the Lu<Subscript>2</Subscript>O<Subscript>3</Subscript>-TiO<Subscript>2</Subscript> system

Nanocrystalline Lu₂O₃-TiO₂ (33.3–44 mol % Lu₂O₃) materials with a partially disordered pyrochlore structure, prepared via heat treatment in the range 1400–1750°C, are found to possess high oxygen ionic conductivity. Their 740°C conductivity is 10^-3 to 10^-2 S/cm, depending on the heat-treatment temperature and composition, which is comparable to that of the well-known fluorite solid electrolyte ZrO₂-9 mol % Y₂O₃.Translated from Neorganicheskie Materialy, Vol. 41, No. 3, 2005, pp. 324–331.Original Russian Text Copyright © 2005 by Shlyakhtina, Mosunov, Stefanovich, Knotko, Karyagina, Shcherbakova.This revised version was published online in April 2005 with a corrected cover date.This revised version was published online in April 2005 with a corrected cover date.     

Lithium ion conductivity of LiLaO<Subscript>2</Subscript>-Li<Subscript>2</Subscript>ZrO<Subscript>3</Subscript> solid solutions

The limits of the LiLaO₂-and Li₂ZrO₃-based solid solutions in the LiLaO₂-Li₂ZrO₃ system have been determined: 0–10 mol % Li₂ZrO₃ and 0–5 mol % LiLaO₂, respectively. We have studied the transport properties (electronic conductivity, temperature and composition dependences of conductivity and activation energy) of lithium lanthanate and the solid solutions in the LiLaO₂-Li₂ZrO₃ system. Conduction in LiLaO₂ is likely due to lithium ion transport through a polyhedral network.     

Phase analysis of the ZrO<Subscript>2</Subscript>-GeO<Subscript>2</Subscript> system

This paper presents a physicochemical study of poorly explored compounds in the zirconia-germania system. Reactions between these oxides were investigated by differential scanning calorimetry and thermogravimetry. The morphology of the reaction products was studied by scanning electron microscopy. The reaction products of ZrO₂ and GeO₂ powders were characterized by quantitative phase analysis. X-ray diffraction and Raman spectroscopy data indicate the formation of the germanates Zr₃GeO₈ and ZrGeO₄. These compounds are shown to be substitutional solid solutions, and their homogeneity ranges are determined. GeO₂ dissolution in ZrO₂ stabilizes its tetragonal structure.     

Properties of nanocrystalline ZrO<Subscript>2</Subscript>-Y<Subscript>2</Subscript>O<Subscript>3</Subscript>-CeO<Subscript>2</Subscript>-CoO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> powders

We have studied the properties of nanocrystalline ZrO₂-Y₂O₃-CeO₂-CoO-Al₂O₃ powders prepared via hydrothermal treatment of a mixture of coprecipitated hydroxides at 210°C. A number of general trends are identified in the variation of the properties of the synthesized powders during heat treatment at temperatures from 500 to 1200°C. Our results demonstrate that the addition of 0.3 mol % CoO to nanocrystalline ZrO₂-based powders containing 1 to 5 mol % Al₂O₃ allows one to obtain composites with good sinterability at a reduced temperature (1200°C).     

Influences of ZrO<Subscript>2</Subscript> nanoparticles on the microstructure and mechanical behavior of Ce-TZP/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanocomposites

Influences of ZrO₂ nanoparticles on the mechanical properties and microstructure of hot-pressing Ce-TZP/Al₂O₃ ceramics were investigated. Meanwhile, t-ZrO₂ to m-ZrO₂ transformation toughening mechanism was investigated by X-ray diffractometry (XRD) method, and deflection of samples under applied stress were recorded too. The results show that when the percentage of ZrO₂ was 20%, the mechanical properties and microstructures of materials are optimum. Moreover, TEM observation show dislocation structures formation both in the Al₂O₃ and on the grain boundary. Because the dislocation agglomeration and fixation by ZrO₂ nanoparticles could deflect cracking or stop cracking development, a strengthening and toughening effect could be achieved.     

Effect of the precipitation sequence on phase formation in the ZrO<Subscript>2</Subscript>-CeO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> system

We have studied phase formation processes during heat treatment of precipitates in the ZrO₂-Al₂O₃ and ZrO₂-CeO₂-Al₂O₃ systems. During heat treatment of powders prepared by coprecipitation of precursors to ZrO₂, CeO₂, and Al₂O₃, α-Al₂O₃ is formed at higher temperatures, which is due to the formation and decomposition of T-ZrO₂ and metastable Al₂O₃ phases. The precipitation sequence in the ZrO₂-CeO₂-Al₂O₃ system influences the lattice parameters of the forming T-ZrO₂-based solid solutions because of the different degrees of Ce⁴⁺ and Al³⁺ substitutions for Zr⁴⁺.     

Preparation and properties of Y<Subscript>2</Subscript>O<Subscript>3</Subscript> partially stabilized ZrO<Subscript>2</Subscript> crystals

We have studied the effect of composition and growth conditions on the structure and properties of 2.5–5 mol % Y₂O₃ partially stabilized ZrO₂ crystals grown by directional solidification in a cold-wall crucible. The phase composition and density of the crystals have been determined. The crystals are shown to be uniform in composition, with local changes in Y₂O₃ content within ±0.5 mol %. The dimensions and quality of the single crystals are influenced by the growth conditions.     

Effect of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> on the properties of nanocrystalline ZrO<Subscript>2</Subscript> + 3 mol % Y<Subscript>2</Subscript>O<Subscript>3</Subscript> powder

We have studied the properties of nanocrystalline ZrO₂〈3 mol % Y₂O₃〉 and 90 wt % ZrO₂〈3 mol % Y₂O₃〉-10 wt % Al₂O₃ powders prepared via hydrothermal treatment of coprecipitated hydroxides at 210°C. The results demonstrate that Al₂O₃ doping raises the phase transition temperatures of the metastable low-temperature ZrO₂ polymorphs and that the structural transformations of the ZrO₂ and Al₂O₃ in the doped material inhibit each other.     

Sorption of U(VI) onto TiO<Subscript>2</Subscript>/ZrO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> Mesoporous Materials from Sulfate Solutions

New nanostructured mesoporous materials of the composition TiO₂/ZrO₂/SiO₂ were prepared by the template sol–gel method using a siloxane–acrylate emulsion as a template. The morphology and structure of these materials and their ability to take up U(VI) were studied. The influence of various factors (ZrO₂ content, pH of solution) on the sorption properties was studied. The suggested materials allow efficient sorption of U(VI) from sulfate solutions with low U(VI) concentrations and can be used in final purification processes.     

A novel method for producing open-cell Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-ZrO<Subscript>2</Subscript> ceramic foams with controlled cell structure

A novel method was introduced to prepare open-cell Al₂O₃–ZrO₂ ceramic foams with controlled cell structure. This method used epispastic polystyrene (EPS) spheres to array ordered templates and centrifugal slip casting in the interstitial spaces of the EPS template to obtain cell struts with high packing density. Aqueous Al₂O₃–ZrO₂ slurries with up to 50 vol.% solid contents were prepared and centrifuged at acceleration of 2,860g. The effect of the solid contents of slurries on segregation phenomena of different particles and green compact uniformity were investigated. In multiphase system, the settling velocities of Al₂O₃ and ZrO₂ particles were calculated. Theory analysis and calculated results both indicated segregation phenomenon was hindered for slurries with 50 vol.% solid content. The cell struts of sintered products had high green density (61.5%TD), sintered density (99.1%TD) and homogeneous microstructures after sintered at 1,550 °C for 2 h. The cell size and porosity of Al₂O₃–ZrO₂ ceramic foams can be adjusted by changing the size of EPS spheres and the load applied on them during packing, respectively. When the porosity increased from 75.3% to 83.1%, the compressive strength decreases from 3.82 to 2.07 MPa.     

Microwave absorption properties of substituted BaFe<Subscript>12</Subscript>O<Subscript>19</Subscript>/TiO<Subscript>2</Subscript> nanocomposite multilayer film

The nanocomposite multilayer film (NCMF) of substituted BaFe₁₂O₁₉ and TiO₂ was prepared using sol-gel method. BaFe_10.5Al_1.5O₁₉, BaFe_10.1Al_1.9O₁₉ and BaFe_11.4Cr_0.6O₁₉ with different absorption frequencies were selected to fabricate the multilayer film with TiO₂. The morphology, crystalline structure and microwave absorption property of the NCMF were investigated with an atomic force microscopy, X-ray diffraction and vector network analyses. The results show that the NCMF is uniform without microcracks and it is an ideal microwave attenuation material with a broad frequency range. Its maximum loss efficiency is about −40 dB. The frequency range with the loss above −10 dB is more than 7 GHz. The multilayer film assembles the achievements of each layer film. Moreover, the compounding of ferrites with TiO₂ is helpful to absorb more microwave energy. TiO₂ particles block the growth of ferrite grains and make most of their size within nanometers. TiO₂ also improves the dielectric loss efficiency of the NCMF.     

Change in the mechanism of conductivity in ZrO<Subscript>2</Subscript>-based crystals depending on the content of stabilizing Y<Subscript>2</Subscript>O<Subscript>3</Subscript> additive

The interrelationship between the structure, phase composition, and transport characteristics of solid electrolytes based on ZrO₂ has been studied as dependent on the content of stabilizing Y₂O₃ additive. It is established that twin boundaries do not lead to the appearance of additional mechanism of ionic conductivity acceleration in ZrO₂–Y₂O₃ crystals. The maximum conductivity has been observed in ZrO₂–(8–10) mol % Y₂O₃ crystals containing a t” phase, in which oxygen atoms are displaced from high-symmetry positions characteristic of the cubic phase.     

Polymorphism of ZrO<Subscript>2</Subscript> nanopowders and mechanochemical synthesis of Zr<Subscript>0.88</Subscript>Sc<Subscript>0.1</Subscript>Ce<Subscript>0.01</Subscript>Y<Subscript>0.01</Subscript>O<Subscript>1.955</Subscript>

The structure of ZrO₂ powders prepared by dehydration of zirconium hydroxide and milling (including techniques with the introduction of grinding additives, such as NaF, CaF₂, diamond, and Cu) was investigated using x-ray powder diffraction and Raman spectroscopy. Samples containing crystallites with the smallest size were synthesized in the presence of copper additives. Ceramic powders of the composition Zr_0.88Sc_0.1Ce_0.01Y_0.01O_1.955 with an improved quality for the use as solid electrolytes in fuel cells were prepared by the mechanochemical synthesis from nanoprecursors and then were characterized. An analysis of the X-ray powder diffraction patterns revealed that the symmetry of the structure of strongly aggregated nanopowders of metastable zirconia increases as a result of twinning, which is favored by a high concentration of vacancies.     

Strain-Induced First-Order Magnetic Phase Transition in Epitaxial Sm<Subscript>0.35</Subscript>Pr<Subscript>0.15</Subscript>Sr<Subscript>0.5</Subscript>MnO<Subscript>3</Subscript> Thin Film

Epitaxial Sm_0.35Pr_0.15Sr_0.5MnO₃ thin films were deposited on LaAlO₃ (LAO, (001)), SrTiO₃ (STO, (001)), and (La_0.18Sr_0.82)(Al_0.59Ta_0.41)O₃ (LSAT, (001)) single-crystalline substrates by using pulsed laser deposition technique. In order to examine the strain effect on electronic and magnetic properties, films were studied by X-ray diffraction, electrical resistivity, and dc magnetization measurements. The film grown on LAO substrate is under compressive strain, and it undergoes ferromagnetic → paramagnetic transition at Curie temperature (T _C) of ～ 165 K and metal → insulator transition at ～ 107 K. The films grown on STO and LSAT substrates are under tensile strain and have T _C of ～ 120 and 130 K, respectively, and show metal → insulator transition at ～ 145 and 137 K, respectively. At T < T _C, the zerofield and fieldcooled magnetization curves of all the films show a huge bifurcation. In the case of films on STO and LSAT substrates, hysteresis is also observed in fieldcooled cooling and warming magnetization vs. temperature measurement protocols at low magnetic field. All the signatures of the firstorder magnetic phase transition are absent in the case of film on LAO substrate. The occurrence and absence of firstorder magnetic phase transition in films on LAO, STO, and LSAT substrates, respectively, have been well explained through the substrateinduced film lattice strain.     

Thermodynamic properties of Dy<Subscript>2</Subscript>O<Subscript>3</Subscript> · 2ZrO<Subscript>2</Subscript> and Ho<Subscript>2</Subscript>O<Subscript>3</Subscript> · 2ZrO<Subscript>2</Subscript> in the range 10–340 K

The low-temperature heat capacity of Dy₂O₃ · 2ZrO₂ and Ho₂O₃ · 2ZrO₂ has been determined by adiabatic calorimetry in the temperature range 10–340 K. The results have been used to calculate the entropy, enthalpy increment, and reduced Gibbs energy of the zirconates without taking into account their low-temperature magnetic transformations.     

Effect of Zr Addition on Bi<Subscript>1.8</Subscript>Pb<Subscript>0.4</Subscript>Sr<Subscript>2.0</Subscript>Ca<Subscript>1.1</Subscript>Cu<Subscript>2.1</Subscript>O<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> Superconductor

The polycrystalline Bi_1.8Pb_0.4Sr_2.0Ca_1.1Cu_2.1 M_xO _y , with M = Zr (x = 0.0, 0.02, 0.04), were synthesized by solid-state reaction method and studied by X-ray diffraction analysis (XRD), scanning electron microscopy equipped with energy dispersive of X-ray analysis (SEM/EDX) and resistivity versus temperature measurements. The influence of the Zr addition on the Tc and microstructure properties of the superconducting compounds has been studied. SEM observations show whiskers grains randomly distributed and microstructural change due to the addition of Zr. The ZrO₂ was incorporated into the crystalline structure of BSCCO system in all samples. The crystallographic structure remains in a tetragonal form where a= b≠c. Generally, all samples exhibit semiconductor behaviour above \(T_{\mathrm {c}}^{\text {onset}}\). The onset critical temperature \(T_{\mathrm {c}}^{\text {onset}}\) increases up to 86 with x = 0.02. There is an enhancement in the critical temperature for doped samples as compared with pure Bi_1.8Pb_0.4Sr_2.0Ca_1.1Cu_2.1O _y .Changes in superconducting properties of ZrO₂ nanoparticle added Bi-2212 system were discussed.     

Microstructure and high-temperature strength of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/Er<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>/ZrO<Subscript>2</Subscript> ternary melt growth composite

A new Al₂O₃/Er₃Al₅O₁₂(EAG)/ZrO₂ ternary MGC (Melt Growth Composite) with a novel microstructure has been fabricated by unidirectional solidification. This ternary MGC has a microstructure consisting of continuous networks of single-crystal Al₂O₃, single-crystal EAG and fine cubic-ZrO₂ phases without grain boundaries. The ternary MGC has also characteristic dimensions of the microstructure of around 2–4 m for EAG phases, around 2–4 m for Al₂O₃ phases reinforced with around 0.4–0.8 m cubic-ZrO₂ phases. No amorphous phases are formed at interfaces between phases in the ternary MGC. The ternary MGCs flexural strength at 1873 K is approximately 700 MPa, more than twice the 330 MPa of the Al₂O₃/EAG binary MGC. The fracture manner of the Al₂O₃/EAG/ZrO₂ ternary MGC at 1873 K shows the same intergranular fracture as the Al₂O₃/EAG binary MGC, but is significantly different from the transgranular fracture of the sintered ceramic.     

Ferromagnetism in Rutile Structure Cr Doped VO<Subscript>2</Subscript> Thin Films Prepared by Reactive-Bias Target Ion Beam Deposition

First generation spintronics has entered the mainstream of information technology through its utilization of the magnetic tunnel junction in applicable devices such as read head sensors for hard disk drives and magnetic random access memory. The future of spintronic devices requires next generation spintronic materials (Wolf et al. in IBM J. Res. Dev. 9:101, [2006]). Here we report on the structural, transport, and magnetic characteristics of V_1−x Cr _x O₂ (0.1≤x≤0.2) thin films deposited on (001) Al₂O₃ substrates. We show that the metal-insulator transition of VO₂ is suppressed and the rutile structure is stable down to 100 K. The films are remarkably smooth having a root-mean squared surface roughness of 0.3 nm. Films are conductive at room temperature and appear to follow a variable-range-hopping conduction mechanism below that. Ferromagnetism is observed at room temperature and is dependent on Cr concentration. The combination of these characteristics makes V_1−x Cr _x O₂ a viable candidate material for next generation spintronic multilayer devices.     

Orientation and microstructure of chemoepitaxial ZrO<Subscript>2</Subscript> films

The orientation and microstructure of ZrO₂ films produced by oxidizing oriented thin Zr films have been studied by transmission electron microscopy and high-energy electron diffraction. The results demonstrate that biaxial textures of the oxide are governed by the textures of the parent zirconium film. We have established a set of orientation relationships between the Zr and ZrO₂ lattices. The nanocrystalline structure of the oxide is due to the fact that there are several equivalent orientations within one Zr grain (multiple-orientation chemoepitaxy). Using high-resolution transmission electron microscopy, we detected twin boundaries, stacking faults, and intragranular dislocations.